Synthetic alcohol



Patented June 25, 1935 2,006,157

V UNITED STATES PATENT OFFICE l r g I 2,000,157 r v smnarrc aLconor.

Benjamin '1. Brooks, Old Greenwich, sem and Reuben Schuler, Elizabeth, N. J., assignors to,

'1 1 Standard Alcohol Company No Drawing. Application December 1,1933, 1 1 I Serial'No.700,611 I 3. Claims. I (cacao-45s) The present invention relates tothe manufacture, a certain amountof ethyl ether is produced. ture of alcohols, and particularly'to an improve- .When the acid mixture "is diluted with waterin ment inth'e adsorption of claims in sulfuricacid proportions equivalent to 60 parts of'water to 40 and their reactions with that. acid. 1 parts by weight of sulfuric acid and the mixture 5 In the manufacture of alcohols from olefins by distilled, the proportion of ether produced; may- '3 the action of sulfuric ,acid of appropriate conbe as'much as l5 parts of ether to 15 parts of centration, the general practice is to dilute the alcohol. acid reaction mixture to hydrolyze the alkyl The ether may be produced in the original sulfates and distill oil the alcohol or alcohols acid reaction mixture before dilution or it may produced. In the manufacture of ethyl and isobe produced during the distillation of the diluted 1o propyl alcohol in this way, substantial propormixture. Whatever may be the explanation of tlons of the ethers, ethyl and di-isopropyl ether, its formation, it is found that in the first stages may be produced. The proportions of ether are of the reaction between the ethylene and the acid greater if relatively little water is used to dilute containing combined ether, the absorption of the the sulfuric acid reaction mixture. Thus dilution ethylene is much more rapid than when using 15 of an ethylene sulfuric acid reaction mixture with acid alone. water to a degree corresponding to 40% sulfuric Since the reaction of the acid with ethylene acid, all the acid being considered as H2504, and is carried out at 80 to 120 (3-, th eth r 00mthen distilling the aqueous solution, gave about pound is partially converted to ethyl sulfuric 2o 15 volumes of ethyl ether to 75 volumes of 95% acid so that the net result of putting back into 90 ethyl alcohol. Di-isopropyl ether is also prothe cycle the ether obtained when the hydrolyzed duced when dilute acid solutions of isopropyl sula id p due i is dis ill i Sub antially to elimfate are distilled. inate ether as a product of the reaction. An ex- In co-pending application Serial No. 700,610, planation Of this r ult may be hat th ether filed December 1, 1933, by Benjamin '1'. Brooks exists in a state of chemical equilibrium either in 25 and Reuben Schuler, it was shown that the con;- the concentrated acid reaction mixture or in version of ethyl ether to ethyl sulfuric acid takes .the diluted acid mixture during distillation. In place when the ether, dissolved in sulfuric acid, y Case, it is W known that distillation of is heated to 80-120 C. when concentrated ethyl sulfuric acid solutions diluted with small sulfuric acid, 93 to 95% H2804. is used, the conproportions of water yield more ether than when 30 version is about 80% complete when the mixture dilu wit large P D ii W There is maintained for two hours at 110 C. is accordingly a substantial saving in sulfuric An object of the present invention i t i acid concentration cost if excessive dilution with crease the yield of alcohols in the reaction of sul- Water is avoidedfuric acid with oleflns, followed by hydroly i There is a substantial proportion, 5 to 10%, 35 while at the same time avoiding the formation of f ether formed v when the acid reaction ethers. product is diluted to 20 parts H2804 to 80 parts According to the present invention, it is found of Water- It is found, w v a by dilut m that sulfuric acid containing relatively small prothe acid reaction product to the equivalent of 40 portions of ethers reacts more rapidly. with the 0 4 Parts Of H2504 to to Part5 Wfl-ter 40 oleflns than the acid without the ethers, and returning the ether formed to successive The ether is probably in the combined form lots of fresh sulfuric acid used in the reaction generally believed to be an oxonium salt or a form with. the ethyl e, ethyl ether 0811 be Substituof addition product which readily yields ether tially eliminated as one of the net or final prodon diluting the acid with water. As has been licks f h pr at t Same im 851111118 the 45 shown in the above mentioned co-pendlng appliadvantage of the more rapid absorption and recation, the conversion of this ether-acid comaction of the ethylene in the early stages of the pound to alkyl sulfuric acid requires an apprereaction.

ciable time at temperatures within the range of The above example is for illustration only as 50 50 and 120 C. the present process may be used in preparing In the conversion of ethylene to ethyl alcohol other alcohols such as isopropyl, isobutyl, etc. by treating it with concentrated sulfuric acid Other strong mineral acids may be used, though followed by hydrolysis of the ethyl or di-ethyl sulsulfuric acid is found to be preferable. The confates and distillation of the hydrolyzed mixcentrations of sulfuric acid used are from 50% u to 100%, higher temperatures being used when weaker acids are used for preparing the acid reaction mixture.

The foregoing description is merely illustrative and alternative arrangement may be made within the scope of the appended claims in which it is our intention to claimall novelty as broadly as the prior art permits.

We claim:

1. In the manufacture of an alcohol, the process which comprises contacting under absorption conditions an olefin with sulfuric acid containing a substantial quantity of an ether.

2. In the manufacture of ethyl alcohol, the process which comprises contacting under absorptionconditions ethylene with sulfuric acid containing at least 10% of ethyl ether.

3. In the manufacture of ethyl alcohol, the process which comprises contacting ethylene with sulfuric acid containing at least 10% of ethyl ether ata temperature between,70 to 110 C.

. 4. In the manufacture of ethyl alcohol, the process which comprises contacting under ab sorption conditions a gas containing ethylene ether.

with sulfuric acid containing a substantial quantity of ethyl ether.

5. In the manufacture of ethyl alcohol, the process which comprises contacting under absorption conditions gas containing ethylene with sulfuric acid containing at least 10% of ethyl ether. I p 6. In the manufacture of ethyl alcohol, the

process which comprises contacting a gas containing ethylene with sulfuric acid containing at least 10% of ethyl ether at a temperature between 70 and 110 C. v

7. In the manufacture of an alcohol, the process which comprisescontacting under absorption conditions an olefin with sulfuric acid of 50% to l00% strength containing at least 10% of an 8. In olefin, the process which comprises forming the alcohol under conditions to produce also an ether, adding to sulfuric acid a substantml quantity of such ether, and utilizing thesulfuric acid to absorb further quantities of the olefin.

- BENJAMIN 'r. Baooxs. V

the manufacture of an alcohol from an 

